Electro-chemical method for selected dissociation



Nov. 25, 1969 O. R. WALTRIF' ELECTROCHEMICAL METHOD FOR SELECTEDDISSOCIATION 3 Sheets-Sheet 1 Filed Oct. 31, 1967 l 36 6.5 in

/////=w ///yL/////W Owen R. Wa/lr/p INVIEIWIORv 9 BY @zmav/fh WAttorney:

Nov. 25, 1969 o. R. WALTRIP 3,430,529

ELECTED-CHEMICAL METHOD FOR SELECTED DISSOCIATION Filed Oct. 31, 1967 3Sheets-Sheet 23 Fig. 3

//////////////////////l/l/l/l l/l// Owen R. Wa/rrip l N V IENTOR.

\\\\\\\\1\ BY Q United States Patent 3,480,529 ELECTRO-CHEMICAL METHODFOR SELECTED DISSOCIATION Owen R. Waltrip, Roseville, Calif., assignorof twentyfive percent to John Konsonlas, ten percent to Paul J. Lunardi,and ten percent to Willis Hampton, all of Roseville, Calif.Continuation-impart of application Ser. No. 497,044, Oct. 18, 1965. Thisapplication Oct. 31, 1967, Ser. No. 679,484

Int. Cl. C0211 1/82; C01d 7/34; B01k 1/00 U.S. Cl. 204-430 9 ClaimsABSTRACT OF THE DISCLOSURE A method for dissociating a medium within atreating zone to recover predetermined elemental components of themedium by establishing a DC. potential within the treating zone,super-imposing oscillating electrical energy, at a radio frequencyvalue, on the DC. potential, and simultaneously imparting oscillatingmechanical energy within the audio frequency range to the mediumentering the treating zone for controlled dissociation of at least aportion of the medium to recover, and thus effectively remove,preselected elemental components of the medium.

This application is a continuation-in-part of application Ser. No.497,044, filed Oct. 18, 1965, now abandoned.

This invention relates to a method, and an exemplary means, fordissociating chemical elements from a medium containing such elements insolution or suspension or consisting of compounds of such elements. Moreparticularly, this invention relates to a method of utilizing an audiofrequency harmonic tone having a predetermined rate of vibrationselected on the basis of the chemical element or elements to bemanipulated, in conjunction with an oscillating electrical energy inputto the medium at a radio frequency value, preferably with thesimultaneous utilization of a reaction promoting D.C. po tential, withina treating zone containing the medium to be acted upon. The presentinvention therefore relates to a method of manipulating chemicalelements by utilizing harmonic audio frequencies complementary to theharmonic wave-energy picture," or more simply state, the harmonic audiofrequency tones corresponding to those naturally radiating from andspecific to each chemical element whereby chemical elements may bemanipulated by utilization of such reproduced harmonic tones whichcorresponds in nature to thermally induced vibrations. Such thermallyinduced vibrations have been long recognized as influencing the rate ofchemical reaction between chemical elements and compounds and has beentheorized as directly related to the newly emerging interpretation bythe scientific community of the harmonic wave energy aspect, or nature,of matter. Thus, the present invention relates to a method of utilizingcombined audio and radio frequency energy, i.e. harmonic wave energy, topromote chemical reactions.

In my copending application referred to hereinbefore I dwell, at somelength, on the theoretical aspects of my interpretation of the harmonicwave energy aspect, or nature, of matter. While it is not my desire tobe restricted to the theory set forth at length therein, or brieflyagain touched upon herein, it will nevertheless be appreciated from thediscussion following hereinafter that the present invention has as itsprimary object the provision of a novel method and means of relating theaforementioned theoretical considerations to the field of chemicalprocesses and apparatus.

In this regard, it is another object of the present invention to providepractical applications of my novel 3,480,529 Patented Nov. 25, 1969method by disclosing exemplary modes of the method such as fordissociating components in a predetermined medium within a treatingzone, comprising a portion of an exemplary apparatus for carrying forthsuch a mode of my invention, whereby a DC. potential is establishedwithin the treating zone, oscillating electrical energy at a radiofrequency value, at a selected variable power input level, i.e., wattageis superimposed on the DC. potential and mechanical energy at an audiooscillating frequency value is imparted to the medium entering thetreating zone.

Exemplary embodiments set forth hereinafter to illustrate the carryingforth of the method of the present invention include the desalinizationof saline water and the purification of domestic or industrial sewagewherein deleterious elemental components are dissociated from, andpreferably recovered from, the medium being treated and wherein theliquid efliuent from the treating zone is mechanically filtered in afiltering apparatus wherein an audio frequency is imposed to keep afiltering membrane therein free from dissociated elemental componentscarried over from the aforementioned primary treating zone therebyproducing a final liquid effiuent of a desired degree of purity.

A further object of the present invention is to provide a novel methodfor dissociating components in a predetermined medium within a treatingzone wherein the medium entering the treating zone has: imparted theretoan audio oscillating frequency of 256 cycles per second whereby in thetreatment of exemplary liquid medium such as saline water, theutilization of such frequency in conjunction with the aforementionedoscillating electrical energy at a radio frequency value preferably inthe presence of a DC. ionizing potential effects the dissociation ofelemental carbon, noble metals, iron and magnesium from the salinewater.

Still another object of the present invention is to provide a novelmethod for dissociating elemental components from saline water so as torender the water suitable for agricultural use by imparting an audiooscillating frequency to the saline water entering a treating zone whichaudio oscillating frequency is the resultant of three audio inputfrequencies of 341 /3, 256 and 426 /3 cycles per second and wherein theaforementioned radio frequency value imposed on the treating zone is ofselectively varied wattage whereby hydrogen, carbon dioxide and oxygenin a gaseous state may be separately and sequentially dissociated fromthe saline water and collected in the gaseous state for subsequentliquefaction, and elemental sodium, carbon and chlorine separately andsequentially collected by selectively varying the wattage of the radiofrequency input.

Still a further object of the present invention is to provide a novelmethod for treating domestic and indus trial sewage to bring about thepurification thereof by the dissociation or degradation of organicsubstances therein to inorganic substances by the elimination ofchemically combined carbon therefrom, and even including the destructionof viable dormant bacteria, by imparting an audio oscillating frequencyconsisting of the resultant of the aforementioned three audio inputfrequencies to sewage entering a treating zone wherein the oscillatingelectrical energy at a radio frequency value imposed on the sewagewithin the treating zone through positive and negative electrodestherein has its polarity reversed at a low rate.

Still a further object of the present invention is to provide anexemplary apparatus for carrying forth the aforementioned exemplaryembodiments of the method of the present invention and wherein suchapparatus is provided with auxiliary components adapted to facilitatethe recovery of and subsequent liquefaction of gaseous componentsevolved from the treating zone as well as an auxiliary filteringapparatus which utilizes radio frequency energy to augment filtration ofliquid efliuent from the primary treating zone.

These together with other objects which will become subsequentlyapparent reside in the method as more fully described hereinafter inconjunction with the apparatus illustrated in the accompanying drawingsforming a part hereof, wherein like numerals refer to like partsthroughout, and in which:

FIGURE 1 is a simplified perspective view of an apparatus constructed inaccordance with the principles of the present invention and primarilyadapted for the treatment of a liquid medium further showing a portionof a gastight cover of the apparatus broken away to show the generalorganization of the major components within the interior of theapparatus.

FIGURE 2 is an enlarged vertical transverse crosssectional view takensubstantially along the plane of the line 22 of FIGURE 1;

FIGURE 3 is an enlarged longitudinal vertical crosssectional view of theapparatus of FIGURE 1 taken substantially along the plane of the line3-3 of FIGURE 1;

FIGURE 4 is a schematic illustration of an auxiliary gaseous componentrecovery means which may be utilized in conjunction with the primarytreatment apparatus of FIGURE 1;

FIGURE 5 is a somewhat schematic view of an auxiliary or secondary,filtration means adapted to be operatively associated with the primarytreatment apparatus of FIGURE 1.

FIGURE 6 is an enlarged cross-sectional view of the osmotic filter ofthe auxiliary apparatus of FIGURE 5 taken substantially along the planeof the line 66 of FIGURE 5; and

FIGURE 7 is a diagrammatic illustration of the major components of theexemplary liquid medium treating apparatus of FIGURE 1 and furthershowing means for generating the audio and radio frequencies requiredfor the carrying forth of the method of the present invention.

Referring now to the drawings in greater detail, and FIGURES 1, 2 and 7in particular, it will be seen that liquid medium treating apparatusindicated generally at 10 therein basically includes a generallyfluid-tight tank 12 and a removable cover 14 sealingly secured to thetank 12 so as to provide a generally fluid-tight enclosure. The interiorof the tank 12 is divided into two chambers by an apertured bulkhead 16provided with a plurality of through apertures 18 to permit liquidmedium introduced into a liquid medium pre-treatment zone 20 defined bythe bulkhead 16 to flow into a liquid medium treating zone comprising asecond chamber indicated generally at 22. In a continuous processingform of the invention, liquid medium is supplied to the pretreatmentchamber 20 through a conduit 24 by a centrifugal pump means 26 receivingliquid medium to be treated through an intake conduit 28. Thepre-treatment chamber 20 is provided with a transducer means 30 adaptedto operate within an audio frequency band to impart mechanical energy tothe medium to be treated and which as seen best in FIGURE 7 receives anaudio frequency input from one or more of three conventional audiofrequency generators 32, 34 and 36 preset to generate a harmonicfrequency and operatively connected to an audio power amplifier 38 whichis in turn connected to the transducer means 30 by a coaxial cable 40which sealingly passes through a side wall of the tank 12.

The treating chamber 22 is provided with a plurality of verticallydisposed longitudinally extending spaced-apart negative and positiveelectrodes indicated generally at 42 and consisting of alternatelydisposed generally negative electrodes 44 such as formed of lead andgenerally positive electrodes 46 such as formed of stainless steel. Thenegative electrodes 44 are connected in parallel by a negative electrodebus bar 48 and the positive electrodes 46 are connected in parallel by abus bar 50. The bus bars 48 and 50 are energized by imposing DC.potential thereon through suitable conductor means indicated generallyat 52 extending from a terminal box 54 receiving a DC. potential inputfrom a suitable generator, not shown, through cable 56 and wherein, asseen best in FIGURES l and 2, the conductor means 52 comprises aplurality of paired conductors 58 connected at a plurality of points 51t0 the respective bus bars 48 and 50 so as to obtain relatively uniformcurrent distribution. The bus bars 48 and 50 are also conductivelyconnected to the output of a radio frequency generator 60 through aradio frequency amplifier 62 connected by lead wires 64 and 66 to thebus bars 48 and 50 through reversing switch means 68. The output energylevel of the radio frequency amplifier 62 is relatively high as comparedto the output of the audio frequency amplifier 38.

The tank 12 is further provided with a discharge outlet 70 incommunication with the treating chamber 22 and wherein the height of theoutlet conduit 70 assists in maintaining the maximum level of liquidmedium within the treating chamber 22 somewhat below the top of theelectrodes 44 and 46, such as indicated in FIGURE 2. From a simultaneousconsideration of FIGURES 1 and 4 it will be seen that the chambers 20and 22 are provided with gas outlets 72 and 74, positioned well abovethe maximum level of liquid within the tank 12, which gas outlets areconnected by a common header 76 to an auxiliary gaseous product recoverymeans indicated generally at 80 which includes a compressor means 82which intakes gaseous components from the header 76 on an intake strokethrough a one-way check valve 84. On its discharge compression stroke,the compressor forces the condensed gaseous components through a one-waycheck valve 86 to a high pressure gas condensing means 88 wherein thehigh pressure gaseous components are condensed to a high pressure liquidwhich liquid is conveyed to a liquid gas storage tank 90 through aone-way check valve 92 and from which storage tank 90 liquefied gas maybe withdrawn as desired by means of a valve means 94.

Now further considering FIGURE 1 in conjunction with FIGURES 5 and 6 itwill be seen that the discharge conduit 70 which conveys the eilluentfrom the treating chamber 22 may be provided with an auxiliaryfiltration means indicated generally at which basically comprises anenclosed tank 102 receiving liquid eflluent from the conduit 70. Thefiltration unit 100 generally comprises a secondary filtration means forthe liquid efiluent of the treating chamber 22. Toward this end, thefiltration unit 100 has operatively positioned within the tank 102thereof an osmotic membrane filter means indicated generally at 104which filter includes a perforated stainless steel cylinder 106 havingan osmotic membrane 108 secured to the exterior thereof and including anannular cylinder of sharp clean filtering sand 110 interposed betweenthe osmotic membrane 108 and a second osmotic membrane 112. The osmoticmembranes and sand are secured to the stainless steel cylinder 106 by adiamond pattern steel mesh fabric 114 secured by a plurality of supportbands 116.

The interior 1123 of the stainless steel tank 106 is connected through aone-way check valve 120, and conduit 122 to a vacuum pump meansindicated generally at 124 which assists in reducing the relativepressure between the interior of the tank 106 and the interior of thetank 102 so as to enhance the passage of liquid medium from within thetank 102 through the osmotic membranes and filtering sand 110 into theinterior 118 of the tank 106 as will be discussed in greater detailhereinafter. In addition, the steel mesh 114 is connected by suitableconductors 126 to the radio frequency generator 60.

The exemplary apparatus briefly discussed hereinabove may be utilizedfor the selected dissociation of innumerable liquid mediums and merelyfor the sake of brevity the discussion hereinafter with regard to theutilization of the above apparatus for the carrying forth of the methodof the present invention will be restricted to the utilization thereoffor the separate treatment of two liquid mediums consisting of salinewater, i.e., sea water, and industrial or domestic sewage. In addition,the treatment of saline water will be discussed with regard to theseparate and sequential recovery of hydrogen, carbon dioxide and oxygengases as well as elemental sodium, carbon and chlorine and alternativelyfor the simultaneous dissociation of elemental carbon, noble metals,iron and magnesium from saline water and the compounds therein.Furthermore, the discussion of the method of the present invention withregard to the treatment of industrial or domestic sewage centersprimarily around the dissociation of organic compounds which it will beappreciated comprise the greatest proportion of contaminants in sewageand wherein for purposes of discussion herein viable organisms such asbacteria, and even including viable dormant bacteria are subjected todissociation and thus irreversible destruction. Thus, the discussion ofthe utilization of the apparatus is intended to specifically set forthexemplary modes of carrying forth the method comprising the presentinvention.

EXAMPLE I In this example, the apparatus described hereinabove isutilized for the dissociation of hydrogen, carbon dioxide, oxygen andchlorine in a gaseous state and the dissociation of sodium, and carbonwhich are collected as solids. In this regard, saline water, such as seawater, is introduced into the tank 12 and thus the compartments 20 and22, to a level somewhat below the top of the electrodes 44 and 46 whichlevel is generally determined by the configuration of the eflluentconduit 70. At this point, and as will best be appreciated from asimultaneous consideration of FIGURES 1 and 7, audio generators 32, 34and 36 are individually energized at 341%, 256 and 426% cycles persecond respectively which three audio frequencies generated comprise theinput to the audio amplifier 38, having a power output range of 1 toapproximately 1000 watts, and wherein the aforementioned threeseparately generated audio frequencies are combined whereby theamplifier 38 has a resultant beat pulse output frequency of 384 cyclesper second which is fed to the transducer 30. The transducer 30 whenintended for operation in a power range of 1 to approximately 20 wattsmost generally is of the crystal type and when intended for operation ina power amplification range of 1 to approximately 1000 watts isgenerally a fully transistorized type. Thus, upon energization of thetransducer 30 in the aforementioned manner mechanical energy at a beatpulse frequency value of 384 cycles per second is imparted to the salinewater within the pretreatment chamber 20. Simultaneously, a DC.potential is applied to the negative and positive electrodes 44 and 46respectively which potential is of a current density conventionallyutilized in electrolytic cells. To complete energization of the treatingapparatus the radio frequency generator 60 is energized and the outputthereof amplified in the radio frequency amplifier 62 which is alsoapplied in a polarized manner to the bars 48 and 50'. The power outputof the amplifier can be as high as 100,000 watts. It will be understoodthat the method of the present invention can be carried forth at apreferred, optimum radio frequency requiring a relatively lower poweroutput of the radio amplifier 62 than when the apparatus 10 is operatedat another less suitable but nonethe-less operative radio frequency. Inthis regard, the preferred radio frequency for this example is 80megacycles. However, since this frequency is within a band allocated tothe United States Marine Corps, the actual tests were conducted atapproximately 27 megacycles which it will be appreciated is within aless stringently regulated citizens band. As discussed hereinabove, theoutput of the amplifier 62 is fed to the bus bars 48 and 50 by means oftheir respective leads 64 and 66. Due to the variable composition of thesaline water being introduced by the pump means 26 the power output ofthe radio amplifier 62 is empirically determined by gradually increasingthe power output until conventional analytical chemical monitoring ofthe gaseous efiluent of the treating zone 22 discharging through theoutlet 74 indicates the presence of the initial component to bedissociated which in this instance generally comprises hydrogen gas. Itwill thus be seen that the saline water energized at a pulse beat audiofrequency of 384 cycles per second in the pre-treating zone 20 passesthrough the apertures 18 in the bulkhead 16 wherein the mechanicallyenergized saline water travels downwardly between the respectiveelectrodes 44 and 46 and the combined effect of the audio frequencyenergy imparted to the water in chamber 20 which it is theorized issomehow coupled with the radio frequency imparted to the liquid medium.traveling through the treating zone 22 effects dissociation of theliquid medium whereby the potential established between the electrodes44 and 46 acts to collect the respective components dissociated. Asindicated hereinabove the hydrogen, for example, is evolved in a gasfraction for subsequent collection, compression and condensing in theapparatus 80. Furthermore, as the power output of the radio amplifier 62is increased and monitoring of the system indicates that the desiredcomponent has become dissociated, the power amplification of the radiofrequency input to the treating zone 22 is maintained at a constantlevel while the volume of saline water being introduced to thepretreatment zone 20 by the pump 26 is maintained at uniform flowwhereby monitoring of the liquid medium in the treating zone 22 by anelectrical meter, not shown, indicates that a minimal potential ispresent in the treating zone. It will be appreciated that the presenceof a minimal potential indicates that there is a nearly complete removalof elements from the saline water that permit the establishment of thepotential between the respective electrodes 44 and 46.

It will be apparent that the treating apparatus 10 is preferablyoperated in a continuous manner. However, it will also be appreciatedthat if so desired the treating apparatus 10 could be operated in abatch manner wherein subsequent to loss of conductivity in the treatingzone 22 the liquid therein would be drained and replaced by additionalamounts of liquid medium to be treated introduced through thepro-treatment zone 20.

Liquid effluent leaving the treating zone 22 through the conduit 70 mayif desired be subjected to the auxiliary filtration apparatus wher inthe diamond steel mesh 144 has a radio frequency value imposed thereon,it having been found unnecessary to reapply the pulse beat audiofrequency which is carried over in the liquid medium so as to keep theouter membrane 112 free from any sludge carried over and repel sodiumand chlorine whereby only pure water passes through to the interior 118of the steel cylinder 106. The vacuum pump means 124 accordinglywithdraws purified water from the interior of the tank 106.

EXAMPLE II The method set forth in Example I was again carried forthutilizing saline water as the medium to be treated with the exceptionthat the treatment was for the dissociation of thecolloidally dispersednoble metals consisting of gold, silver, mercury, platinum, palladium,iridium, rhodium, ruthenium and osmium, as well as iron and magnesiumand to effect dissociatio of carbon, th fore bringing about thedegradation of any organic compound in the saline water. In carrying outthe dissociation of this example the audio frequency input to thetransducer 30 consists solely of the output of audio generator 34, whichas indicated heretofore, generates a harmonic audio frequency of 256cycles per second. The over-all operation of the treating apparatus 10and the ancillary treating means 80 and 100 was the same as set forthwith regard to Example 1.

EXAMPLE III In still another test involving the utilization of thetreating apparatus 10 to carry forth the method of the present inventionsubstantially untreated sewage, comprising a mixture of industrial anddomestic sewage obtained from a municipal sewage plant, was treated byin troducing the sewage into the pre-treatment chamber whereinmechanical energy was imparted thereto by subjecting the influent to aresultant beat pulse of 384 cycles per second to the transducer 30 whichbeat pulse was a resultant of the combined outputs of audiogenerators32, 34 and 36 operating at 341 /3, 256, and 426% cycles persecond respectively combined into a beat pulse and amplified by theaudio frequency amplifier 38. As in Example I, the negative electrodes44 and positve electrodes 46 had a D.C. potential applied thereacrossthrough the paired leads 58 operatively and conductively connected to asource of D.C. current as discussed hereinabove and wherein the positivelead 66 of the radio frequency amplifier 62 was connected to the bus bar50 and the negative lead 54 from the radio frequency amplifier 62connected to the bus bar 48. For test purposes only a frequency of 27megacycles was used. From the foregoing it will be seen that theoperation of the treating apparatus 10 for the treatment of sewage issubstantially the same as that utilized in Example I for the treatmentof saline water for the desalinization thereof and/or separate recoveryof several other components thereof. However, to effect dissociation ofthe organic compounds, i.e. the bulk of the contaminants in sewage andincluding viable dormant bacteria, the radio frequency polarityreversing switch operatively interposed in the output leads 64 and 66 ofthe radio amplifier 62, is utilized to reverse the polarity of the radiofrequency energy applied to the bus bars 48 and 50, and thus theelectrodes 44 and 46. The reversing was carried out at a low rate, i.e.,a few times per minute, whereby the liquid effluent leaving the treatingzone 22 through the discharge conduit 70 had an exceptionally lowB.O.D., only a trace of settleable solids and actually exhibited anincrease in dissolved oxygen apparently due to liberation of oxygen fromthe organic compounds dissociated. The efiluent also had an extremelylow density of coliform organisms per unit of efliuent. It will beappreciated of course that with the utilization of a relatively simpletreating apparatus as shown herein the device would of necessity have tobe shutdown periodically to remove the carbonaceous precipitateresulting from the dissociation of the organic compounds, whichprecipitate will eventually bring a halt to the dissociation actionwithin the treating zone 22. When treating sewage in the aforementionedmanner, it has also been found to be desirable to operate the ancillaryharmonic frequency-osmotic filter means 100 to insure removal of anyminute amounts of sludge, i.e. carbonaceous material, carried over fromthe primary treating zone 22. In such case, the harmonicfrequency-osmotic filter means 100 is operated substantially as setforth hereinabove to effect final filtration of the efiluent of theprimary treating zone 22.

Thus, from the foregoing it will be understood that the method of thepresent invention apparently permits the coupling of a key harmonicfrequency or key harmonic frequencies to a radio frequency carrier in aliquid medium simultaneously subjected to a D.C. potential wherein thedissociation of elemental components contained in the liquid medium maybe readily effected.

The foregoing is considered as illustrative only of the principles ofthe invention. Further, since numerous modifications and changes willreadily occur to those skilled in the art, it is not desired to limitthe invention to the exact construction and operation shown anddescribed, and accordingly all suitable modifications and equivalentsmay be resorted to, falling within the scope of the invention asclaimed.

What is claimed as new is as follows:

1. A method for dissociating components in a predetermined medium withina treating zone comprising the steps of: establishing a D.C. potentialwithin the treating zone; superimposing oscillating electrical energy onsaid potential at a radio frequency value; and imparting mechanicalenergy to the medium entering the treating zone at an audio oscillatingfrequency.

2. The method of claim 1 wherein said audio oscillating frequency is 256cycles per second.

3. The method of claim 1 wherein said audio oscillating frequency is theresultant of three audio input frequencies of 341 /3, 256 and 426 /3cycles per second.

4. The method of claim 1 including the step of: reversing the polarityof said potential relative to the superimposed electrical energy at arate less than the audio frequency of the mechanical energy.

5. The method of claim 1 including the step of withdrawing gasesreleased in the treating zone from the medium.

6. The method of claim 5 wherein said audio oscillating frequency is 256 cycles per second.

7. The method of claim 5 wherein said audio oscillating frequency is theresultant of three audio input frequencies of 341 /3, 256 and 426 /3cycles per second.

8. The method of claim 1 including the step of filtering the mediumafter withdrawing from the treating zone.

9. The method of claim 8 including the step of: reversing the polarityof said potential relative to the superimposed electrical energy at arate less than the audio frequency of the mechanical energy.

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2,585,103 2/1952 Fitzgerald 2l0l9 X 72,861,932 11/1958 Pohl 204273 X2,907,455 10/1959 Sasaki 2l0l9 X 3,109,721 11/1963 Zenner et al 21019 X3,206,397 9/1965 Harvey 21019 3,266,631 8/1966 Snaper 210-19 X 3,294,66612/1966 Wiersma 204228 3,305,481 2/1967 Peterson 21019 ALLEN B. CURTIS,Primary Examiner US. Cl. X.R.

